TW202000632A - Alicyclic diol and method for producing same - Google Patents

Abstract

Provided are an alicyclic diol represented by formula (1), a method for producing the same, and the like.

Description

Alicyclic diol and its manufacturing method

The invention relates to an alicyclic diol with a paraffin ring and a method for manufacturing the same.

Alicyclic diols are used as raw materials for polymers such as (meth)acrylic urethane resins, polyester resins, polycarbonate resins, and polymers synthesized using alicyclic diols as raw materials. Optical materials, electronic information materials, coating materials, adhesive/adhesive materials, etc. For example, Patent Document 1 discloses that (meth)acrylic acid urethane using norbornane-2,2-dimethanol as an alicyclic diol. In addition, Patent Document 2 discloses a modified polyester using tricyclodecane-2,2-dimethanol as an alicyclic diol. Furthermore, Patent Document 3 discloses the use of decahydro(1,4:5,8-dimethylene naphthalene-2,6-diyl) dimethanol (isomer purity 99.5%) as an alicyclic diol Of polycarbonate resin. However, the above-mentioned polymers are not necessarily sufficient, so new polymers excellent in heat resistance, optical properties, storage elastic modulus, hardness, etc. are sought. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 10-45702 [Patent Document 2] Japanese Patent No. 3790553 [Patent Document 3] International Publication No. 2016/052370 Specification

[Problems to be solved by the invention]

The purpose of the present invention is to provide a novel alicyclic diol having a drop-alkane ring and a method for manufacturing the same. [Technical means to solve the problem]

表示。 [2]一種式(1)

所表示之脂環式二醇之製造方法，其特徵在於：使式(2)

所表示之四環[4.4.0.1^2,5 .1^7,10 ]-3-十二烯氫醛化，繼而於布忍斯特鹼之存在下，與甲醛反應。 [3]一種聚酯多元醇，其係藉由使如[1]之脂環式二醇與二元酸反應而獲得。 [4]一種(甲基)丙烯酸胺基甲酸酯單體，其係藉由使如[3]之聚酯多元醇與二異氰酸酯化合物、繼而與羥基(甲基)丙烯酸酯化合物反應而獲得。 [5]一種(甲基)丙烯酸胺基甲酸酯樹脂，其係藉由使如[4]之(甲基)丙烯酸胺基甲酸酯單體硬化而獲得。 [發明之效果]The present invention provides the following [1] to [5]. [1] An alicyclic diol of formula (1)

Said. [2] One formula (1)

The method for producing the alicyclic diol shown is characterized by formula (2)

Represented by the tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene hydroformylation hydrogen, followed in the presence of Brønsted base Lancaster, the reaction with formaldehyde. [3] A polyester polyol obtained by reacting an alicyclic diol as in [1] with a dibasic acid. [4] A (meth)acrylate urethane monomer obtained by reacting a polyester polyol as in [3] with a diisocyanate compound, and then with a hydroxy (meth)acrylate compound. [5] A (meth)acrylic urethane resin obtained by curing the (meth)acrylic urethane monomer as in [4]. [Effect of invention]

According to the present invention, it is possible to provide a novel alicyclic diol having a drop-alkane ring and a method for manufacturing the same.

所表示之化合物。以下，將式(1)所表示之化合物稱為化合物(1)。對於其他式編號之化合物亦相同。 本發明之化合物(1)可具有任意立體結構，可為具有單一立體結構者，又，亦可為其等之混合物。 本發明之化合物(1)可作為(甲基)丙烯酸胺基甲酸酯樹脂、聚酯樹脂、聚碳酸酯樹脂等聚合物之原料而使用，藉由使用化合物(1)作為原料，可獲得耐熱性、光學特性、儲存彈性模數、硬度等優異之聚合物。此種聚合物之用途無特別限定，例如可列舉：光學材料、電子資訊材料、塗佈材料、黏著/接著材料等。Hereinafter, preferred embodiments of the present invention will be described in detail. The alicyclic diol of the present invention is formula (1)

The compound represented. Hereinafter, the compound represented by formula (1) is referred to as compound (1). The same is true for compounds of other formula numbers. The compound (1) of the present invention may have any three-dimensional structure, may have a single three-dimensional structure, or may be a mixture thereof. The compound (1) of the present invention can be used as a raw material for polymers such as (meth)acrylate urethane resins, polyester resins, polycarbonate resins, etc. By using the compound (1) as a raw material, heat resistance can be obtained It is a polymer with excellent performance, optical properties, storage modulus and hardness. The use of such polymers is not particularly limited, and examples include optical materials, electronic information materials, coating materials, and adhesive/adhesive materials.

所表示之四環[4.4.0.1^2,5 .1^7,10 ]-3-十二烯進行氫醛化反應，藉此獲得式(3)

所表示之3-甲醯基甲基四環[4.4.0.1^2,5 .1^7,10 ]十二烷，繼而使所獲得之化合物(3)於布忍斯特鹼之存在下，與甲醛反應。氫醛化反應於觸媒及一氧化碳與氫之混合氣體之存在下進行。Compound (1) can be produced by using formula (2)

Represented by the tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene hydrogen hydroformylation reaction, thereby obtaining the formula (3)

Represented by the 3-acyl-methyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodecane, and then the obtained compound (3) in the presence of a Brønsted base of Manchester, with formaldehyde . The hydroformylation reaction is carried out in the presence of a catalyst and a mixed gas of carbon monoxide and hydrogen.

The compound (2) can be commercially available, or can be produced according to a known method. In the case of manufacturing according to a well-known method, for example, it can be reduced by the method described in SB Soloway, J. Am. Chem. Soc., 1952, 74(4), pp 1027-1029 Diene is produced by Diels-Alder reaction. In the hydroformylation reaction of the compound (2), a catalyst used in a general hydroformylation reaction, for example, a well-known metal catalyst such as a cobalt-based catalyst, a rhodium-based catalyst, and a platinum-based catalyst can be used. Among them, in terms of reaction rate and yield, etc., a cobalt-based catalyst or a rhodium-based catalyst is preferred. As the above-mentioned metal catalyst, a metal carbonyl complex compound, any compound that can form a metal carbonyl complex compound in the reaction system, etc. can be used. Furthermore, a metal catalyst supported on an appropriate carrier such as silicone or activated carbon can also be used Media. Specific examples of such metal catalysts include the above-mentioned metal oxides, acetylpyruvate, various carboxylates, sodium salts, chlorides, carbonyl complexes, triphenylphosphine complexes, etc., More specifically, Co ₂ (CO) ₈ , Co ₄ (CO) ₁₂ , Co ₆ (CO) ₁₆ , NaCo(CO) ₄ , CoH(CO) ₄ , [Co(CO) ₃ (C ₅ H ₅ )] ₂ (where C ₅ H ₅ represents cyclopentadienyl), cobalt oxide, cobalt acetate, cobalt 2-ethylhexanoate, Rh ₄ (CO) ₁₂ , Rh ₆ (CO) ₁₆ , acetic acid Rhodium, rhodium 2-ethylhexanoate, rhodium stearate, Rh(acac) ₃ (where acac represents acetone. The same applies below), Rh(acac)(CO) ₂ , Rh(acac)(cod ) (Wherein cod represents 1,4-cyclooctadienyl), RhCl ₃ , RhCl(PPh ₃ ) ₃ , (where Ph represents phenyl. The same applies below), RhH(CO)(PPh ₃ ) ₃ Wait. These metal catalysts can be used alone or in combination of two or more. In terms of reaction rate, economy, etc., when the rhodium catalyst is used, the catalyst concentration is usually 0.1 to 1000 ppm, preferably 0.5 to 500 ppm, based on the weight concentration of rhodium atoms in the reaction mixture. It is preferably in the range of 1 to 100 ppm. In terms of reaction speed, economy, etc., when the cobalt catalyst is used, the catalyst concentration is usually 10 to 5000 ppm, preferably 50 to 4000 ppm, based on the weight concentration of cobalt atoms in the reaction mixture. More preferably, it is in the range of 100 to 3000 ppm.

In addition, with respect to these catalysts, an excessive amount of organic phosphorus compounds can coexist. The organic phosphorus compound is not particularly limited, and examples thereof include a phosphine represented by the general formula R ¹ ₃ P and a phosphite represented by the general formula (R ² O) ₃ P. The three R ¹ and the three R ² may be the same or different, and examples include aromatic hydrocarbon groups, aliphatic hydrocarbon groups, and the like. Specifically, it is not particularly limited, and examples thereof include: alkyl groups having 1 to 12 carbon atoms; phenyl groups which may be substituted with alkyl groups having 1 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, or sulfonyl groups; C1-C8 alkyl group or C1-C8 alkoxy substituted alicyclic alkyl group, etc. Here, examples of the alicyclic alkyl group include cyclohexyl group and the like. In addition, bicyclic heterocyclic phosphines can also be used. More specifically, triphenylphosphine, tricresylphosphine, tris(2-methylphenyl)phosphine, sodium triphenylphosphine trisulfonate, tricyclohexylphosphine, tri-n-butylphosphine, 9 -Phosphabicyclo[3.3.1]nonane, 8,9-dimethyl-2-phosphabicyclo[3.3.1]nonane, 2-phosphabicyclo[3.3.1]nonane, triphenylphosphite Ester, tris(nonylphenyl) phosphite, tris(2-third butylphenyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, tris( 2-methylphenyl) ester, tris(3-methyl-6-tert-butylphenyl) phosphite, tris(3-methoxy-6-tert-butylphenyl) phosphite, etc. Among these, triphenylphosphine or triphenylphosphite is preferred. These organic phosphorus compounds may be used alone or in combination of two or more. In terms of catalyst life, reaction selectivity, etc., the use amount of these organic phosphorus compounds relative to metals (rhodium, cobalt, etc.) is usually 1 to 2000 mole times, preferably 3 to 1000 mole times, More preferably, it is in the range of 5 to 500 mole times.

The hydroformylation reaction may be carried out without using a solvent, or a solvent may be used. The solvent is not particularly limited as long as it dissolves the raw material olefin, the metal catalyst, and the organic phosphorus compound. Specific examples include alcohols such as ethanol, 2-propanol, 1-butanol, 2-ethylhexanol, and 2-octanol, butyl acetate, cyclohexyl acetate, and dibutyl phthalate. , Di(2-ethylhexyl) phthalate, diisononyl phthalate, diisodecyl phthalate, triisononyl trimellitate, pentane, hexane , Heptane, octane, isooctane, isononane, decane, dodecane, tetradecane and other saturated aliphatic hydrocarbons, cyclohexane, methylcyclohexane, dimethylcyclohexane, cyclo Alicyclic hydrocarbons such as octane, cyclododecane, decahydronaphthalene, aromatic hydrocarbons such as benzene, toluene, xylene, alkylnaphthalene, ethers such as dibutyl ether, tetrahydrofuran, nitriles such as acetonitrile and propionitrile Class etc. These solvents may be used alone or in combination of two or more. The temperature of the hydroformylation reaction is usually 40 to 180°C, preferably 60 to 170°C, and more preferably 80 to 160°C. If it is carried out at a temperature of 40°C or higher, the reaction rate is increased, so it is more desirable. Furthermore, if it is carried out at a temperature of 180° C. or lower, the amount of by-products generated is reduced, and the yield of the reaction is increased, which is more desirable.

The hydroformylation reaction is preferably performed under pressurization using a mixed gas of carbon monoxide and hydrogen (hereinafter, referred to as synthesis gas). At this time, carbon monoxide and hydrogen may be independently introduced into the reaction system, or a synthesis gas may be prepared in advance and introduced into the reaction system. The molar ratio (=CO/H ₂ ) of the synthesis gas introduced into the reaction system is usually 0.2 to 5.0, preferably 0.5 to 2.0, and more preferably 0.7 to 1.5. Furthermore, gases that are inert to the hydroformylation reaction, such as methane, ethane, propane, nitrogen, helium, argon, carbon dioxide, etc., may coexist in the reaction system. The hydroformylation reaction is usually preferably carried out at a pressure in the range of 0.2 to 40 MPaG. For example, when a catalyst precursor is used instead of an organic phosphorus compound, the pressure is usually 10 to 30 MPaG, preferably 15 to 28 MPaG, and more preferably 18 to 26 MPaG. By setting the pressure to 10 MPaG or more, the catalyst is more stabilized and a sufficient reaction speed is obtained. In addition, by setting the pressure to 30 MPaG or less, it is possible to further reduce the cost of equipment with excellent pressure resistance, which is preferable. On the other hand, when the organic phosphorus compound and the catalyst precursor are used in combination, the pressure is usually 0.3 to 30 MPaG, preferably 0.5 to 20 MPaG, and more preferably 0.7 to 10 MPaG. By setting the pressure to 0.3 MPaG or more, the catalyst is more stabilized, and a sufficient reaction speed is obtained. In addition, by setting the pressure to 20 MPaG or less, it is possible to further reduce the cost of equipment with excellent pressure resistance, which is preferable.

The reaction form of the hydroformylation reaction is not particularly limited, and it can be carried out in batch mode using a known reaction device, or continuously. Specifically, it can be implemented by any one of a stirred reaction tank, a tower reaction tank, or a tube type reaction tank. The mixture containing the compound (3) obtained after the hydroformylation reaction of the compound (2) can be used directly as a raw material for the next step, or it can be purified by a well-known method. The raw material for the next step. As the refining method in the case of refining by a known method, for example, methods such as adsorption or extraction, neutralized water washing, distillation, and crystallization can be used, or these methods can be used in appropriate combination. In the case of using a cobalt-based catalyst, it is preferably subjected to a neutralization and washing step, for example, after the hydroformylation reaction is completed, the cobalt-based catalyst is extracted and removed by adding an aqueous solution of an alkali metal compound or an alkaline earth metal compound to the system catalyst. Examples of the alkali metal compound or alkaline earth metal compound include hydroxides and metal salts of lithium, sodium, potassium, magnesium, and calcium.

Examples of the formaldehyde used in the production of the compound (1) from the compound (3) include paraformaldehyde, trioxane, and formaldehyde aqueous solution. In terms of reactivity, paraformaldehyde or trioxane are preferred. . The amount of use is converted to formaldehyde, and is preferably 2 to 4 mole times relative to compound (3), more preferably 2.5 to 3 mole times. Examples of the brunster base used in the production of compound (1) from compound (3) include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, and alkaline earths such as calcium hydroxide and barium hydroxide The carbonates such as metal hydroxides, sodium carbonate, and potassium carbonate are preferably sodium hydroxide or potassium hydroxide in terms of reactivity and price. These brunster bases can be used alone or in combination of two or more. The use amount of the brunster base relative to the compound (3) is preferably 1 to 2 mole times, more preferably 1.2 to 1.6 mole times. The addition method of the Brunnest base is not particularly limited, and in terms of controlling the reaction temperature, it is preferably dissolved in a solvent and then added dropwise. When producing compound (1) from compound (3), a solvent may also be used. The solvent is not particularly limited as long as it does not hinder the reaction, and examples thereof include alcohols such as methanol, ethanol, 2-propanol, 1-butanol, 2-ethylhexanol, and 2-octanol, pentane, Saturated aliphatic hydrocarbons such as hexane, heptane, octane, isooctane, isononane, decane, dodecane, tetradecane, aromatic hydrocarbons such as benzene, toluene, xylene, dibutyl ether, Ethers such as tetrahydrofuran, nitriles such as acetonitrile, propionitrile, etc. These solvents may be used alone or in combination of two or more. The reaction temperature when producing the compound (1) from the compound (3) is usually 10 to 80°C, preferably 30 to 70°C. If the reaction temperature is 10°C or higher, the reaction rate is increased, and if it is 80°C or lower, the fear of formaldehyde volatilization becomes less, which is more desirable. The reaction pressure when the compound (1) is produced from the compound (3) is not particularly limited, and in terms of simplification of the reaction apparatus, it is preferably normal pressure. In addition, from the viewpoint of preventing deterioration of the compound (3) in the air, the reaction is preferably carried out in an atmosphere of an inert gas, and more preferably in a nitrogen atmosphere.

The mixture containing the compound (1) obtained after the reaction can be removed by removing the aqueous layer containing the formate, and then adding water to the organic layer to wash with water to remove residual formic acid, brunster base, and formaldehyde. The mixture containing the compound (1) obtained after the reaction can be purified by a known method to isolate the compound (1). As the purification method, for example, methods such as adsorption, extraction, distillation, and crystallization may be used, or these methods may be appropriately combined and used. When the mixture containing the compound (1) is purified by crystallization, a solvent is used, and as a solvent, it is not particularly limited as long as it does not react with the mixture containing the compound (1) during crystallization, and examples include methanol, ethanol, and Alcohols such as 2-propanol, 1-butanol, 2-ethylhexanol, 2-octanol, ethyl acetate, butyl acetate, cyclohexyl acetate and other esters, pentane, hexane, heptane, Saturated aliphatic hydrocarbons such as octane, isooctane, isononane, decane, dodecane, tetradecane, aromatic hydrocarbons such as benzene, toluene, xylene, ethers such as dibutyl ether, tetrahydrofuran, acetonitrile , Propionitrile and other nitriles, water, etc. These solvents may be used alone or in combination of two or more.

The compound (1) of the present invention can be used as a raw material to produce a polymer, such as a (meth)acrylate urethane resin or a polyester resin. The polymer obtained from the compound (1) can be a material excellent in heat resistance, optical characteristics, storage elastic modulus, hardness and the like. The use of the material having such characteristics is not particularly limited, and examples thereof include optical materials, electronic information materials, coating materials, and adhesive/adhesive materials. When the compound (1) of the present invention is used as a raw material to produce a (meth)acrylic acid urethane resin, it can be produced by a method according to a known method, for example, Japanese Patent No. 06- The method described in Gazette No. 27156, after producing a polyester polyol by reacting a compound (1) with a dibasic acid, reacts with a diisocyanate compound, and then a hydroxy (meth)acrylate compound to produce (methyl) Acrylic urethane monomer, and harden the obtained monomer.

The above-mentioned polyester polyol can be produced, for example, by reacting the compound (1) with a dibasic acid within a range of 120 to 300° C. for 5 to 60 hours. As the dibasic acid used in the production of the polyester polyol, general dibasic acids, for example, known dibasic acids such as aromatic, aliphatic, and alicyclic can be used. Specific examples of such dibasic acids include adipic acid, phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, succinic acid, oxalic acid, propylene Diacid, glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, cyclopropanedicarboxylic acid, cyclohexanedicarboxylic acid, dodecanedioic acid, hexahydrophthalic anhydride, Dimer acid, etc. The use amount of these dibasic acids is not particularly limited, and it is preferably 0.5 to 1.0 mole times relative to the compound (1). In the production of the above polyester polyol, a catalyst may also be used. Examples of the catalyst include tetraisopropyl orthotitanate, tetra-n-butyl orthotitanate, diethyl tin oxide, and dibutyl tin oxide. Zinc oxide, etc. As the weight concentration in the reaction mixture, for example, a catalyst can be used at 0.1 to 1000 ppm. The polyester polyol preferably has a hydroxyl value of 5 to 120 mgKOH/g and a number average molecular weight of 1,000 to 20,000.

In the case of producing the (meth)acrylic acid urethane monomer using the polyester polyol as a raw material, for example, it can be produced by setting the polyester polyol and the diisocyanate compound at 50 The reaction is performed in the range of -150°C for 2 to 20 hours, and further reacted with the hydroxy (meth)acrylate compound in the range of 50 to 150°C for 2 to 20 hours. When manufacturing the (meth)acrylic urethane monomer, the polyester polyol may be used alone or in combination with a known polyol. Specific examples of known polyols include ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, and 3-methyl-1, 5-pentanediol, 2,4-diethyl-1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol , 2-butyl-2-ethyl-1,3-propanediol, 1,9-nonanediol, 1,4-cyclohexanedimethanol, tricyclodecanedimethanol, and 2,2'-bis( 4-hydroxycyclohexyl) propane and other polyester polyols obtained by reacting with the dibasic acid exemplified as the dibasic acid in the production of the polyester polyol; polytetramethylene ether glycol, polyethylene glycol , Polyether polyols such as polypropylene glycol; polyolefin polyols such as polybutadiene polyol and polyisoprene polyol; polycarbonate polyol; polycaprolactone polyol and so on.

As the diisocyanate compound when manufacturing the (meth)acrylic acid urethane monomer, any of known isocyanates of aromatic, aliphatic, alicyclic, etc. having two isocyanate groups can be used . Specific examples of such diisocyanate compounds include 4,4′-diphenylmethane diisocyanate, terephthalic diisocyanate, tolyl diisocyanate, 1,5-naphthalene diisocyanate, xylylene diisocyanate, Hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, bis(isocyanatomethyl)cyclohexane, norane diisocyanate, naphthalene diisocyanate, etc. Examples of the hydroxy (meth) acrylate compound when manufacturing the (meth) acrylate carbamate include 2-hydroxy ethyl (meth) acrylate, 2-hydroxy propyl (meth) acrylate, 1,9-nonanediol mono(meth)acrylate, propylene oxide modified mono(meth)acrylate, caprolactone modified mono(meth)acrylate, trimethylolethane di(meth) Group) acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, 1,4-butanediol mono(meth)acrylate, 4-hydroxy(meth)acrylate Cyclohexyl ester, 1,6-hexanediol mono(meth)acrylate, neopentyl glycol mono(meth)acrylate, etc.

When the above polyester polyol is reacted with a diisocyanate compound, and then reacted with a hydroxy (meth)acrylate compound, a catalyst may also be used. As the catalyst, for example, triethylene diamine and triethyl Amines, 1,8-diazabicyclo(5,4,0)-undecene-7 (DBU), dibutyltin dilaurate, dimethyloctyltin, etc. Based on the weight concentration in the reaction mixture, the catalyst can use 0.1-1000 ppm. The reaction with a hydroxy (meth) acrylate compound can be carried out in the presence of a polymerization inhibitor for the purpose of inhibiting free radical polymerization during the reaction. Examples of the polymerization inhibitor include benzoquinone and butylated hydroxytoluene , Hydroquinone, hydroquinone monomethyl ether, third butyl catechol, third butyl hydroquinone, etc. The polymerization inhibitor can be added in an amount of 0.01 to 2% by weight relative to the polyester polyol, and when used together with oxygen, the polymerization inhibitory effect can be improved. The molar ratio of the diisocyanate compound and the hydroxy (meth) acrylate compound to the polyester polyol as the raw material of the (meth) acrylate carbamate monomer is not particularly limited, and preferably 1.0 to 3.0 and 1.0～4.0. In the production of polyester polyols and (meth)acrylate urethane monomers, solvents can also be used. Examples of solvents include benzene, toluene, xylene, hexane, isohexane, heptane, and isooctane. Alkane, isononane, methyl ethyl ketone, methyl isobutyl ketone, etc. These solvents may be used alone or in combination of two or more.

By hardening the (meth)acrylate urethane monomer, a (meth)acrylate urethane resin can be produced. In this case, the (meth)acrylate urethane monomer may be used alone, or may be used in combination with a known monofunctional or polyfunctional (meth)acrylic monomer. Examples of the curing method include an electron beam curing method, an ultraviolet curing method, a thermal curing method, and other known methods, and any method can be used. When using an ultraviolet curing method, for example, by adding a photopolymerization initiator of 0.1 to 15% by weight to a (meth)acrylate carbamate monomer, such as benzophenone-based or acetylphosphine oxide-based, and irradiating ultraviolet rays And harden it.

When the compound (1) of the present invention is used as a raw material to produce a polyester resin, it can be produced by the following two-stage reaction: The first-stage reaction is based on a well-known method such as Japanese Patent Laid-Open No. 2013- The method described in 227384 is to directly esterify the dibasic acid with the compound (1), or to perform a transesterification reaction between the lower alkyl ester of a dibasic acid such as dimethyl dibasic acid and the compound (1) to produce di The polyol ester and/or its oligomer of the metaacid; and the reaction in the second stage, and then the reaction product obtained in the first stage is heated under reduced pressure, and the polycondensation reaction is carried out until the desired degree of polymerization is reached. As the dibasic acid in the dibasic acid and the lower alkyl ester of the dibasic acid in the production of the polyester resin, a general dibasic acid such as aromatic, aliphatic, and alicyclic known dibasic can be used acid. Specific examples of such dibasic acids include phthalic acid, isophthalic acid, terephthalic acid, naphthalene dicarboxylic acid, anthracene dicarboxylic acid, biphenyl dicarboxylic acid, and 4,4′-dicarboxylic acid. Diphenyl ether dicarboxylic acid, 4,4'-diphenylmethane dicarboxylic acid, 4,4'-diphenylbenzene dicarboxylic acid, 4,4'-diphenylisopropylidene dicarboxylic acid, cis Adipic acid, fumaric acid, succinic acid, oxalic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, cyclopropane dicarboxylic acid, cyclic Hexanedicarboxylic acid, dodecanedioic acid, hexahydrophthalic anhydride, dimer acid, etc. When producing the above polyester resin, the compound (1) of the present invention may be used alone or in combination with a known polyol. Specific examples of known polyols include ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, and 3-methyl-1, 5-pentanediol, 2,4-diethyl-1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol , 2-butyl-2-ethyl-1,3-propanediol, 1,9-nonanediol, 1,4-cyclohexanedimethanol, tricyclodecanedimethanol, 2,2'-bis(4 -Hydroxycyclohexyl) propane and the like. [Example]

Hereinafter, the present invention will be further specifically described by examples and the like, but the present invention is not limited to the following examples and the like. The purity of the products obtained in the examples was analyzed by a gas chromatograph with a hydrogen flame ion detector, and the identification was performed by gas chromatography mass spectrometry and ¹ H-NMR. In the production example, the progress of the reaction was confirmed by measuring the acid value, hydroxyl value, and NCO value.

[Gas chromatograph with hydrogen flame ion detector] <Measurement conditions> ・Device: Gas chromatograph GC-14B manufactured by SHIMADZU ・Column: HP-5 manufactured by Agilent Technologies (Column length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm) ・Temperature increase conditions: After maintaining at 60°C for 0.5 minutes, increase the temperature at a rate of 15°C per minute to 320°C, and maintain for 17 minutes. ・Temperature of sample injection part and detector: 320℃

[Gas chromatography mass spectrometry] <Measurement conditions> ・Device: Gas chromatograph 6890N manufactured by Agilent ・Device: Mass spectrometer JMS-K9 manufactured by JEOL ・Column: DB-5 manufactured by Agilent Technologies (Column length 30 m, inner diameter 0.25 mm, film thickness 0.25 μm) ・Temperature increase conditions: After maintaining at 60°C for 0.5 minutes, increase the temperature at a rate of 15°C per minute to 320°C, and maintain for 17 minutes. ・Temperature of sample injection part and detector: 320℃ ・Ion source: CI (chemical ionization)

[ ¹ H-NMR] <Measurement conditions> • Device: JNM-ECA500 manufactured by JEOL Ltd. • Measurement solvent: dimethyl sulfoxide-d6 99.9% Contains 0.05 Vol% tetramethylsilane • Resonance frequency: 500 MHz

[Acid Value] Measured according to the method of JIS K 0070:1992. Accurately weigh 0.1 to 3 g of the sample in a 200 ml conical flask, and dissolve it in a solution of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.)/2-propanol (manufactured by Wako Pure Chemical Industries, Ltd.) = 4/1. Using phenolphthalein as an indicator, a 0.1 mol/L potassium hydroxide ethanol solution (for volume analysis, manufactured by Wako Pure Chemical Industries, Ltd.) was used for neutralization titration to calculate the acid value.

[Hydroxyl value] Measured according to the method of JIS K 0070:1992. Measure 12.5 g of acetic anhydride (manufactured by Wako Pure Chemical Industries, Ltd.) in a 50 ml volumetric flask and make a fixed volume with pyridine (manufactured by Wako Pure Chemical Industries, Ltd.) to prepare an acetylating agent. Accurately weigh 1.0 g of the sample in a 200 ml conical flask, take 5 ml of the acetylating agent with a full pipette, add it to the sample, and heat at 100°C for 1 hour. After leaving to cool, pipette 1 ml of water and 5 ml of pyridine with a full pipette, rinse the inner wall while adding to the sample, and heat at 100°C for 10 minutes. After leaving to cool, 5 ml of ethanol (manufactured by Wako Pure Chemical Industries, Ltd.) was measured with a full pipette, and added to the sample while rinsing the inner wall. Using phenolphthalein as an indicator, a 0.5 mol/L potassium hydroxide ethanol solution (for volume analysis, manufactured by Wako Pure Chemical Industries, Ltd.) was used for neutralization titration to calculate the hydroxyl value.

[NCO value] Measured according to the method of JIS K 1603-1:2007. Measure 0.646 g of di-n-butylamine (manufactured by Wako Pure Chemical Industries, Ltd.) in a 50 ml volumetric flask and make a volume with tetrahydrofuran (super-dehydrated, manufactured by Wako Pure Chemical Industries, Ltd.) to prepare a di-n-butylamine solution. Accurately weigh 0.1 to 3 g of the sample in a 200 ml conical flask, add 25 ml of tetrahydrofuran (super dehydration) and 5 ml of di-n-butylamine solution, and let stand for 15 minutes. 50 ml of 2-propanol (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and bromocresol green (0.04% acetone solution) was used as an indicator to titrate with 0.1 mol/L hydrochloric acid solution to calculate the NCO value.

[Example 1] [Production of compound (3)] In a 500 ml autoclave, compound compound (2) (manufactured by Tokyo Chemical Industry Co., Ltd.) 300.0 g (1.87 mol) and triphenyl phosphite were added at room temperature (Kanto Chemical Co., Ltd.) 0.58 g (1.87 mmol) and Rh(acac)(CO) ₂ (NECHEMCAT Co., Ltd.) 0.0048 g (0.0187 mmol), and the inside was replaced with nitrogen. The temperature in the system was raised to 50°C, and while maintaining this temperature, it was stirred for 10 minutes. After that, the interior was replaced with a synthesis gas (mole ratio of CO/H ₂ = 1) and the pressure was increased to 5.0 MPaG, then the temperature in the system was raised to 90°C, the temperature and pressure were maintained, and the reaction was stopped after 5 hours to obtain Compound (3) 344.6 g. The analysis by a gas chromatograph with a hydrogen flame ion detector revealed that the purity of the obtained compound (3) was 94.5%. Based on the compound (2), the yield was 96.7%.

[Production of Compound (1)] In a 1000-ml four-necked flask equipped with a Dairy condenser and a dropping funnel, 180.0 g (0.95 mol) of compound (3) and 1-butanol (and After manufacturing 180.0 g of Kodak Pharmaceutical Co., Ltd. and 72.0 g (2.40 mol) of paraformaldehyde (manufactured by Wako Pure Chemical Co., Ltd.), 50% by weight of potassium hydroxide aqueous solution was added dropwise thereto at a reaction temperature of 40° C. for 2 hours ( 130.0 g (potassium hydroxide 1.16 mol) was prepared from potassium hydroxide and water manufactured by Tim Chuan Chemical Co., Ltd., and then heated to 60° C. and stirred for 5 hours. After standing, the water layer was removed, and washing with 100.0 g of water was carried out three times while keeping the liquid temperature at 50°C. The solvent was distilled off from the obtained organic layer, and isononane (manufactured by KH NEOCHEM) was added thereto to precipitate a solid, which was crystallized from isononane using ethanol (manufactured by Japan Alcohol) to obtain a compound ( 1) 128.7 g. Analysis by a gas chromatograph with a hydrogen flame ion detector showed that the purity of the compound (1) obtained was 99.9% or more, and the yield was 61.2% based on the compound (3). The measurement was performed by gas chromatography mass spectrometry (CI), and as a result, a peak of 223 [(M+H) ⁺ ] which was consistent with the compound (1) was confirmed. The results of ¹ H-NMR measurement are shown below. ¹ H-NMR (DMSO-d ₆ , δppm); 4.43 (1H), 4.17 (1H), 3.70 (2H), 3.25 (1H), 3.12 (1H), 2.18 (2H), 2.13 (1H), 2.06 ( 1H), 1.93 (1H), 1.79-1.72 (2H), 1.70-1.60 (2H), 1.48 (2H), 1.03-0.96 (3H), 0.90 (1H), 0.63 (1H)

[Example 2] [Manufacture of polyester polyol] 50.0 g (0.23 mol) of compound (1) and 27.8 g (0.19 mol) of adipic acid (manufactured by Wako Pure Chemical Industries, Ltd.) were added to a multi-necked flask with a volume of 200 ml. After raising the temperature to 130°C to melt the compound (1) and adipic acid, the inside was replaced with nitrogen. The temperature in the system was raised to 220°C, and the pressure was reduced to 40 kPa. The generated water was extracted while reacting for 9 hours. Thereafter, 0.0040 g of tetra-n-butyl orthotitanate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the reaction was further performed for 6 hours. The acid value was confirmed to be below 0.3 mgKOH/g, and the reaction was completed. After the reaction was completed, 1.7 g of 0.1% phosphorous acid/ethanol solution (phosphorous acid: manufactured by Wako Pure Chemical Industries, Ltd., ethanol: manufactured by Wako Pure Chemical Industries, Ltd.) was added to the system and stirred at 130°C for 1 hour, followed by 130 The low boiling point components were distilled off at 2 kPa at ℃ to obtain 59.7 g of polyester polyol. The acid value of the obtained polyester polyol is 0.1 mgKOH/g, and the hydroxyl value is 49.8 mgKOH/g. Moreover, the number average molecular weight calculated from the obtained hydroxyl value was 2253.

[Example 3] [Manufacture of acrylic urethane monomer] In a separable flask with a volume of 200 ml, add 50.0 g (22.2 mmol) of the polyester polyol obtained in Example 2, methyl ethyl ketone (super dehydrated, manufactured by Wako Pure Chemical Industries, Ltd.) 41.3 g, and Hydroquinone monomethyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.026 g (0.21 mmol). After heating to 60°C to dissolve the polyester polyol, the inside was replaced with nitrogen. After that, the system was left to cool to 40°C, isophorone diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) 9.8 g (44.1 mmol) was added, the temperature in the system was raised to 60°C, and dibutyltin dilaurate (Tokyo) was added Chemical Industry Co., Ltd.) 0.016 g (0.025 mmol), and methyl ethyl ketone (Super Dehydration, Wako Pure Chemical Industries Co., Ltd.) 0.56 g. The temperature in the system was raised to 70°C, the temperature was maintained, and the reaction was carried out for 4 hours. Then, after the system was left to cool to room temperature, air bubbling was carried out, and 2-hydroxyethyl acrylate (Wako Pure Chemical Industries, Ltd.) was added to the residual NCO group in the system calculated based on the NCO value of 41.2 mmol. After manufacturing) 4.8 g (40.9 mmol), the temperature in the system was raised to 70°C. The reaction was continued while maintaining this temperature, and the reaction was terminated after 11 hours to obtain an urethane acrylate monomer.

[Example 4] [Manufacture of acrylic urethane resin] To the acrylic urethane monomer obtained in Example 3, methyl ethyl ketone (super dehydrated, manufactured by Wako Pure Chemical Industries, Ltd.) was added , Adjust so that the solid content becomes 50%, add 2% by weight of α-hydroxybenzophenone (Omnirad184, manufactured by TOYOTSU CHEMIPLAS), and stir. The obtained liquid composition was applied to a substrate (polypropylene plate or zinc phosphate steel plate) by a film applicator, and UV curing was performed under the following conditions, followed by heating and drying at 100° C. for 3 hours. Irradiation energy: 270～280 mV/cm ² , conveyor belt speed: 850 rpm, irradiation frequency: 10 times

[Reference Example 1] [Production of polyester resin] In a multi-necked flask with a volume of 200 ml, 20.0 g (90 mmol) of compound (1) and dimethyl terephthalate (manufactured by Tokyo Chemical Industry Co., Ltd.) 35.0 g ( 180 mmol), ethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.) 8.4 g (135 mmol), tetra-n-butyl orthotitanate (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.006 g. After raising the temperature to 150°C to melt the compound (1) and dimethyl terephthalate, the inside was replaced with nitrogen. The temperature in the system was raised to 230°C, and methanol produced was extracted while reacting for 10 hours. Thereafter, while gradually raising the temperature and reducing the pressure to 280°C and 0.1 kPa, the reaction was continued for 12 hours. After the reaction was completed, it was left to cool to room temperature to obtain 39.9 g of polyester resin. The molecular weight of the obtained polyester was analyzed by gel permeation chromatography. As a result, the weight average molecular weight was 28,000, the number average molecular weight was 17,000, and the dispersion index was 1.6. Furthermore, the introduction ratio of the polyol component into the polyester resin was analyzed by ¹ H-NMR, and as a result, the compound (1)/ethylene glycol=40/60.

[Test example] [Measurement of glass transition temperature (Tg)] The "Differential Scanning Calorimeter DSC-220" manufactured by Hitachi High-Tech Science Co., Ltd. was used in accordance with the method of JIS K 7121:1987. For the acrylic urethane resin obtained in Example 4, the test piece (film thickness: 160 μm) produced on the polypropylene plate was finely pulverized and added to the measurement container. Under a nitrogen atmosphere, the temperature was raised to 110°C at a heating rate of 10°C/min, held for 10 minutes, and then melted, then quenched at 10°C/min to 40°C, and then cooled to -50°C, and then again at a heating rate of 10°C/min The temperature was raised to 110°C, and the glass transition temperature at this time was determined. For the polyester resin obtained in Reference Example 1, the resin was finely pulverized and added to the measurement container. Under a nitrogen atmosphere, the temperature was raised to 190°C at a heating rate of 10°C/min, held for 10 minutes, and then melted. After quenching at 40°C/min to -50°C, the temperature was raised to 250°C again at a heating rate of 10°C/min. , Find the glass transition temperature at this time.

[Measurement of refractive index and Abbe number] Using the "Abbe Refractometer DR-M2" manufactured by Atago Corporation, the measurement was performed according to the method of JIS K 7142:2014. Using bromonaphthalene as an intermediate liquid, the refractive index at 23°C and 589 nm of a test piece (film thickness: 160 μm) produced on a polypropylene plate was measured. In addition, the refractive index at 486 nm, 589 nm, and 656 nm was measured to calculate the Abbe number.

[Determination of storage elastic modulus] The "Dynamic Viscoelastic Device DVE-V4" manufactured by UBM was used for measurement in accordance with JIS K 7244-4:1999. Under the air atmosphere, the dynamic viscoelasticity of the test piece produced on the polypropylene plate was measured under the following conditions to obtain the storage elastic modulus at 40°C. Frequency: 10 Hz, test piece size: 15 mm×5 mm (film thickness: 160 μm) Measuring temperature: 30℃～200℃, heating rate: 2℃/min

[Measurement of pencil hardness] Measured according to the method of JIS K 5600-5-4:1999. For test pieces (film thickness: 80 μm) made on zinc phosphate steel plates, use pencils of each hardness of 2 B to 2 H, and pressurize them sequentially with a load of 750 g from the lower hardness to perform pencils Determination of hardness. Visually check for damage, and set the hardness immediately before the damage to the pencil hardness.

由表1可知，實施例4中所獲得之丙烯酸胺基甲酸酯樹脂之耐熱性、光學特性優異，儲存彈性模數、鉛筆硬度亦較高。因此，使用化合物(1)作為原料之丙烯酸胺基甲酸酯樹脂可期望用作耐熱性、光學特性、儲存彈性模數、硬度等優異之光學材料、電子材料、塗佈材料、黏著/接著材料等。 [產業上之可利用性]Table 1

It can be seen from Table 1 that the acrylic urethane resin obtained in Example 4 is excellent in heat resistance and optical characteristics, and also has high storage elastic modulus and pencil hardness. Therefore, the urethane acrylate resin using the compound (1) as a raw material can be expected to be used as an optical material, electronic material, coating material, adhesive/adhesive material excellent in heat resistance, optical characteristics, storage elastic modulus, hardness, etc. Wait. [Industry availability]

The alicyclic diol obtained in the present invention is useful as a raw material for polymers used in optical materials, electronic information materials, coating materials, adhesive/adhesive materials, and the like.

1 is a ¹ H-NMR spectrum of the compound obtained in Example 1. FIG.

Claims (5)

An alicyclic diol, which is represented by formula (1)

Said. One formula (1)

The method for producing the alicyclic diol shown is characterized by formula (2)

Represented by the tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene hydroformylation hydrogen, followed in the presence of Brønsted base Lancaster, the reaction with formaldehyde. A polyester polyol obtained by reacting an alicyclic diol as described in claim 1 with a dibasic acid. A (meth)acrylate carbamate monomer obtained by reacting the polyester polyol as claimed in claim 3 with a diisocyanate compound and then with a hydroxy (meth)acrylate compound. A (meth)acrylic urethane resin obtained by hardening the (meth)acrylic urethane monomer according to claim 4.

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